Separation agent comprising acyl- or carbamoyl-substituted polysaccharide

ABSTRACT

Separation of a chemical substance is effected by treating a mixture thereof with a polysaccharide having a substituent for hydroxyl group an acyl group of the formula (1) or a carbamoyl group of the formula (2): ##STR1## wherein R represents an atomic group having a nucleus comprising a conjugated π-bond system in which the number of bonds interposed between an atom contained therein and bonded with the carbonyl or amino group and an atom contained in the π-bond system and most distant from said atom is at least 5 even in the shortest route.

This application is a divisional application of U.S. Ser. No.07/246,449, filed Sept. 19, 1988, now U.S. Pat. No. 4,879,038, which isa continuation-in-part of U.S. Ser. No. 716,791, filed Mar. 27, 1985,now abandoned.

The invention relates to a separation agent which comprises apolysaccharide derivative having an acyl or a carbamoyl group as asubstituent for a hydroxyl group. It has a conjugated π-bond system. Theseparation agent of the invention is useful for separation of variouschemical substances, especially optical resolution of optical isomers.In addition, it serves for separation of geometrical isomers andpolymers having different molecular weight ranges from each other. Theyhave not easily been separated in the state of the prior art.

The resolving agent of the present invention can be used for separationof all sorts of chemical substances, particularly for optical resolutionof them.

It has been well known that optical isomers of a chemical compound haveeffects different from each other in vivo generally. Therefore, it is animportant problem to obtain chemically pure compounds for the purposesof improving medicinal effects per unit dose of the compounds orremoving adverse reactions thereof and damage from them in medical,agricultural and biochemical fields. A mixture of optical isomers hasbeen optically resolved by preferential crystallization process ordiastereomer process. However, varieties of the compounds capable ofbeing optically resolved by these processes are limited and theseprocesses require a long time and much labor. Under these circumstances,development of a technique of conducting the optical resolution by aneasy chromatographic process has eagerly been demanded.

Chromatographic optical resolution has been investigated from old times.However, resolving agents developed heretofore have problems that theyhave only an unsatisfactory resolution efficiency, compounds to beresolved should have a specific functional group or their stability isonly poor. Thus, it has been difficult to optically resolve all sorts ofcompounds with satisfactory results.

An object of the present invention is to provide a resolving agenthaving a chemical structure different from those of known resolvingagents and, therefore, resolving characteristics different from those ofthe known ones or a higher faculty of discriminating and identifying theoptical isomers.

Particularly, the asymmetric structure of the polysaccharide isamplified by modifying it with a substituent having a sufficient lengthso as to obtain a higher faculty of identifying optical isomers.

The above-mentioned object of the present invention is attained by anagent for separation which contains as an effective component apolysaccharide derivative having as a substituent an acyl group of thefollowing formula (1) or a carbamoyl group of the following formula (2):##STR2## wherein R represents an atomic group having a nucleuscomprising a conjugated π-bond system in which the number of bondsinterposed between an atom contained therein and bonded with thecarbonyl or amino group and an atom contained in the π-bond system andmost distant from said atom is at least 5 even in the shortest route.

The resolving agent of the invention exhibits preferably differentpowers of adsorbing different optical isomers of a given compound.

In the identification of the asymmetric structure of a cellulosederivative such as cellulose tribenzoate or cellulosetrisphenylcarbamate, an asymmetric space formed by adjacent substituentson C₂ and C₃ of the cellulose may contribute most greatly to theidentification. Therefore, the inventors thought that the enlargement ofsaid space would increase the faculty of identifying optical isomers.After intensive investigations, the inventors have found surprisinglythat the polysaccharide derivatives having the above-mentionedsubstituents have quite excellent faculty of identifying opticalisomers. The present invention has been completed on the basis of thisfinding.

The term "polysaccharide" herein involves any optically activepolysaccharide selected from the group consisting of synthetic, naturaland modified natural polysaccharides. Among them, those having highlyregular bonds are preferred. Examples of them include β-1, 4-glucans(celluloses), α-1, 4-glucans (amylose and amylopectin), α-1, 6-glucan(dextran), β-1, 6-glucan (pustulan), β-1, 3-glucans (such as curdlan andschizophyllan), α-1, 3-glucan, β-1, 2-glucan (Crown gallpolysaccharide), β-1, 4-galactan, β-1, 4-mannan, α-1, 6-mannan, β-1,2-fructan (inulin), β-2, 6-fructan (levan), β-1, 4-xylan, β-1, 3-xylan,β-1, 4-chitosan, β-1, 4-N-acetylchitosan (chitin), pullulan, agarose andalginic acid. Still preferred ones are those capable of easily yieldinghighly pure polysaccharides, such as cellulose, amylose, β-1,4-chitosan, chitin, β-1, 4-mannan, β-1, 4-xylan, inulin and curdlan.

These polysaccharides have a number-average degree of polymerization(average number of pyranose or furanose rings in the molecule) of atleast 5, preferably at least 10. Though there is provided no upper limitof the degree of polymerization, it is preferably 500 or less from theviewpoint of easiness of the handling.

In the substituents of the polysaccharide derivatives of the followingformulae according to the present invention: ##STR3## R represents anatomic group comprising a conjugated π-bond system having at least agiven length and capable of conjugation with the carbonyl orcarboxyamino group. The term "at least a given length" herein means thatthe number of bonds interposed between an atom bonded the carbonyl orcarboxyamino group and an atom contained in the conjugated π-bond systemand most distant from said atom is at least 5 in even the shortestroute. The term "π-bond system" refers to not only usual double andtriple bonds, but also lone electron pairs and vacant orbitals capableof conjugation with them. For example, in a p-methoxybenzoate group ofthe following formula: ##STR4## the conjugated π-bond systemcorresponding to R is conjugated with the carbonyl group. However, inthis structure, the number of bonds interposed between an atom bondedwith the carbonyl group, i.e., C₁, and an atom contained in theconjugated π-bond system and most distant from said atom (C₁), i.e., anoxygen atom of the methoxy group, is 4. Therefore, this structure is notincluded in the present invention. Examples of R included in theinvention are as follows:

(1) substituted phenyl group such as those shown below: ##STR5##

(2) phenylethenyl and phenylethynyl groups: ##STR6##

(3) condensed aromatic ring and condensed hetero aromatic ring groupssuch as those shown below: ##STR7##

(4) condensed quinones such as those shown below: ##STR8## as well assubstituted derivatives of them. The number, position and variety of thesubstituents are not particularly limited.

30 to 100%, preferably 85 to 100%, of the hvdroxyl groups of thepolysaccharides forming the derivatives should be acylated orcarbamoylated in the present invention. The balance of the hydroxylgroups may be present in the form of free hydroxyl groups or they may beesterified, etherified or carbamoylated so far as the resolving capacityof the resolving agent is not damaged.

When a styryl or phenyl group is introduced into a cellulose or amylosetriphenylcarbamate derivative, a high liquid-crystallizability orcrystallizability is expectable, since the side chains are arrangedregularly and the rigidity of the main chain is increased. Therefore, itwas believed that these triphenyl derivatives might have an interestingoptical resolution power.

Since an interesting change in the optical resolution power was observedwhen chloroform was added to the eluent, the effect of using chloroformwith these polysaccharide derivatives was also investigated.

It also was believed that when ##STR9## is introduced into position 4 ofa cellulose triphenylcarbamate derivative, the conjugated system of thephenyl group would become larger and the characteristics of the sidechain as the mesogenic group would become more remarkable. On the basisof this idea, cellulose tris[4-(2-phenylethynyl)phenylcarbamate] wasexamined with respect to its optical resolution power.

The optical resolution powers of triphenylcarbamates having an phenoxygroup as a substituent also were investigated.

To synthesize the polysaccharide derivative used in the presentinvention, a corresponding polysaccharide is pretreated suitably, ifnecessary, and then reacted with an acylating agent or carbamoylatingagent. The acylating agents include usually corresponding acid halides,acid anhydrides and mixed anhydrides with other strong acids. Usually,the reaction is conducted in the presence of a catalyst comprising atertiary amine, particularly pyridine or an acidic substance. Thecarbamoylating agents include usually corresponding isocyanates. Thereaction proceeds easily in the presence of a catalyst comprising atertiary amine or a Lewis acid. In producing mixed derivatives, thesubstituted polysaccharide is reacted with these reagents or,alternatively, the polysaccharide is reacted with these reagents andthen with other esterifying, etherifying or carbamoylating agent (see,for example, "Dai-Yuki Kagaku", 'Tennen Kobunshi Kagaku I and II",published by Asakura Book Store, and R. L. Whistler "Methods inCarbohydrate Chemistry" III, IV and V, published by Academic Press).

The resolving agent of the present invention is used for the purpose ofresolving compounds and optical isomers thereof generally according to achromatographic method such as gas, liquid or thin layer chromatographicmethod. Further, the resolving agent may be used in membrane resolutionmethod.

In using the resolving agent of the present invention in liquidchromatography, there may be employed a method wherein the powderedresolving agent is packed in a column, a method wherein a capillarycolumn is coated with the resolving agent, a method wherein a capillaryis made from the resolving agent to use the inner wall thereof and amethod wherein the resolving agent is spun and bundled up to form acolumn. Among them, the method wherein the powdered resolving agent isemployed is most general.

The resolving agent is powdered preferably by crushing or by formingbeads. The particle size which varies depending on the size of a columnor plate used is 1 μm to 10 μm, preferably 1 to 300 μm. The particlesare preferably porous.

It is preferred to support the resolving agent on a carrier so as toimprove the durability thereof to pressure, to prevent swelling orshrinkage thereof due to solvent exchange or to reduce the number oftheoretical plates. The suitable size of the carrier which variesdepending on the size of the column or plate used is generally 1 μm to10 μm, preferably 1 to 300 μm. The carrier is preferably porous and hasan average pore diameter of 10 Å to 100 μm, preferably 50 to 50,000 Å.The amount of the resolving agent to be supported is 1 to 100 wt. %,preferably 5 to 50 wt.%, based on the carrier.

The resolving agent may be supported on the carrier by either chemicalor physical means. The physical means includes one wherein the resolvingagent is dissolved in a suitable solvent, the resulting solution ismixed with a carrier homogeneously and the solvent is distilled off bymeans of a gaseous stream under reduced pressure or heating and onewherein the resolving agent is dissolved in a suitable solvent, theresulting solution is mixed homogeneously with a carrier and the mixtureis dispersed in a liquid incompatible with said solvent by stirring todiffuse the solvent. The resolving agent thus supported on the carriermay be crystallized, if necessary, by heat treatment or the like.Further, the state of the supported resolving agent and accordingly itsresolving power can be modified by adding a small amount of a solventthereto to temporarily swell or dissolve it and then distilling thesolvent off.

Both porous organic and inorganic carriers may be used, though thelatter is preferred. The suitable porous organic carriers are thosecomprising a high molecular substance such as polystyrene,polyacrylamide or polyacrylate. The suitable porous inorganic carriersare synthetic or natural products such as silica, alumina, magnesia,titanium oxide, glass, silicate or kaolin. They may be surface-treatedso as to improve their affinity for the resolving agent. The surfacetreatment may be effected with an organosilane compound or by plasmapolymerization.

In liquid or thin layer chromatography, any developer may be used exceptthose in which the resolving agent is soluble or which are reactive withthe resolving agent. In case the resolving agent has been bound to thecarrier by the chemical process or it has been insolubilized bycrosslinking, any solvent other than a reactive liquid may be used. As amatter of course, it is preferred to select the developer afterexamination of various developers since the resolving characteristics ofchemical substances or optical isomers vary depending on the developerused.

In the thin layer chromatography, a layer having a thickness of 0.1 to100 mm and comprising the resolving agent in the form of particles ofabout 0.1 μm to 0.1 mm and, if necessary, a small amount of a binder isformed on a supporting plate.

In the membrane resolution process, the resolving agent is used in theform of a hollow filament or film.

(Effects of the invention)

The resolving agent of the present invention containing thepolysaccharide having an acyl or carbamoyl substituent as the effectivecomponent is effective for the resolution of various compounds.Particularly, it is quite effective for the resolution of opticalisomers which are quite difficult to resolve. Either one of the opticalisomers to be resolved is selectively adsorbed on the resolving agent.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a graph showing the chromatographic resolution oftranscycloprcpanedicarboxylic acid dianilide on a column using anamylose tris(4-styrylphenylcarbamate) packing.

DETAILED DESCRIPTION OF THE INVENTION

The remarkable effects of the resolving agents of the present inventionare apparent from comparison of separation factor α obtained in thefollowing examples with those of conventional cellulose resolvingagents.

For example, in the optical resolution of trans-stilbene oxide accordingto chromatography using a mixture of hexane and 2-propanol in a ratio of9:1 as the eluent, the α value obtained when cellulose tri-β-naphthoatewas used was 1.58 which was far higher than the α value of 1.42 obtainedwhen cellulose tribenzoate, i.e., a known cellulose resolving agent, wasused. In the optical resolution of Troger's base, through the highest αvalue obtainable with known cellulose resolving agents was 1.40(obtained with tribenzylcellulose, a higher α value can be obtained withthe resolving agent of the present invention. More particularly, αvalues of 2.82, 1.84 and 1.42 are obtained with cellulose tricinnamate,trisbiphenylcarboxylate and trisphenylazobenzoate, respectively. Fromthis fact, the effects of the substituents in the resolving agent of thepresent invention are evident.

The following examples will further illustrate the present invention,which by no means limit the invention. In the examples, the terms aredefined as follows: ##EQU1##

SYNTHESIS EXAMPLE 1

10 grams of silica beads (Lichrospher SI 1000; a product of Merck & Co.)was placed in a 200 ml round-bottom flask with a side arm. Aftervacuum-drying in an oil bath at 120° C. for 3 hours, N₂ was introducedtherein. 100 ml of toluene which had been preliminarily distilled in thepresence of CaH₂ was added to the silica beads. 3 ml ofdiphenyldimethcxysilane (KBM 202; a product of Shin'etsu Kagaku Co.,Ltd.) was added to the mixture and they were stirred together and thenreacted at 120° C. for 1 hour. After distilling off 3 to 5 ml oftoluene, the reaction was carried out at 120° C. for 2 hours. Themixture was filtered through a glass filter, washed with 50 ml oftoluene three times and then with 50 ml of methanol three times anddried in vacuo at 40° C. for 1 hour.

About 10 grams of the silica beads were placed in the 200 mlround-bottom flask with a side arm. After vacuum drying at 100° C. for 3hours, the pressure was returned to atmospheric pressure and the mixturewas cooled to room temperature. Then, N₂ was introduced therein. 100 mlof distilled toluene was added to the dried silica beads. 1 ml of N,O-bis (trimethylsilyl) acetamide (a trimethylsilylating agent) was addedthereto and the mixture was stirred to effect the reaction at 115° C.for 3 hours. The reaction mixture was filtered through a glass filter,washed with toluene and dried in vacuo for about 4 hours.

SYNTHESIS EXAMPLE 2

Cellulose triacetate (a product of Daicel Ltd.) having a number-averagedegree of polymerization of 110 and a degree of substitution of 2.97 wasdissolved in 1 liter of acetic acid (a product of Kanto Kagaku Co.). 5.2ml of water and 5 ml of conc. sulfuric acid were added to the resultingsolution and the reaction was carried out at 80° C. for 3 hours. Thereaction mixture was cooled and sulfuric acid was neutralized with anexcess aqueous magnesium acetate solution. The resulting solution wasadded to 3 liters of water to precipitate cellulose triacetate having areduced molecular weight. After filtration and collection with a glassfilter (G3), it was dispersed in 1 liter of water. After filtrationfollowed by vacuum drying, the obtained product was dissolved inmethylene chloride and reprecipitated from 2-propanol. The dissolutionand the reprecipitation were repeated twice to effect the purification.The product was dried. According to the IR and NMR spectra, the productwas identified as cellulose triacetate. The number-average molecularweight of the product as determined by vapor pressure osmometry was7900, which corresponded to the number-average degree of polymerizationof 27. The vapor pressure osmometry was conducted with a vapor pressureosmometer Corona 117 using a solvent mixture of chloroform/1% ethanol.

60 grams of the obtained cellulose triacetate was dispersed in 200 ml of2-propanol. 60 ml of 100% hydrazine hydrate (a product of Nakarai KagakuCo.) was added dropwise slowly to the dispersion under gentle stirring.The suspension was maintained at 60° C. for 3 hours and the resultingcellulose was filtered through a glass filter, washed with acetonerepeatedly and vacuum-dried at 60° C. In the IR spectrum of the product,no absorption band due to the carbonyl group at around 1720 cm⁻¹ wasobserved and the IR spectrum coincided with that of cellulose.

SYNTHESIS EXAMPLE 3 Synthesis of cellulose tris-4-biphenylcarboxylate)

10 ml of pyridine and 3 ml of triethylamine were added to 0.7 grams ofthe cellulose obtained in above Synthesis Example 2, 7.0 grams of4-biphenylcarbonyl chloride (a product of Aldrich Co.) and 0.02 grams ofdimethylaminopyridine. The mixture was kept at 90° C. under stirring for5 hours. 10 ml of benzene was added thereto and the obtained mixture waskept at 90° C. for 1.5 hours. The dark brown reaction liquid was addedto 200 ml of ethanol. The formed precipitates of the cellulose esterwere filtered through a glass filter (G3), washed with ethanol and thenacetone repeatedly and dried in vacuo to obtain 2.6 grams of theproduct. In its IR spectrum, characteristic absorptions were observed at3020, 3050, 1720, 1605, 1260, 1100, 860, 740 and 700 cm⁻¹ and nostretching vibration of a 740 and 700 cm hydroxyl group was observed.This fact suggested that the product was a trisubstituted compound.

SYNTHESIS EXAMPLE 4 (Synthesis of cellulose tris-p-phenylazobenzoate)

51.5 ml of dehydrated pyridine, 5.7 ml of dehydrated triethylamine and37 mg of 4-dimethylaminopyridine were added to 1.1 grams of thecellulose obtained in Synthesis Example 2. 15.8 grams ofp-phenylazobenzoyl chloride was added thereto under stirring and thereaction was carried out at 100° C. for 5 hours. After cooling, theproduct was added to 400 ml of ethanol under stirring to formprecipitates. After filtration through a glass filter, the precipitateswere washed thoroughly with ethanol. After drying in vacuo, the productwas dissolved in 30 ml of methylene chloride. After removal of insolublematter, the product was reprecipitated from 400 ml of ethanol. Theprecipitates were filtered, washed with ethanol, dehydrated and dried toobtain 5.2 grams of cellulose tris-p-phenylazobenzoate. This product wasdissolved in methylene chloride and the solution was applied to a sodiumchloride tablet and dried. The infrared absorption spectrum of theproduct had the following characteristic absorption bands:

3050 cm⁻¹ : stretching vibration of aromatic C--H,

1740 cm⁻¹ : stretching vibration of C═O of carboxylic acid ester,

1610, 1490, 1450 and 1420 cm⁻¹ : skeletal vibration due to stretching ofcarbon and carbon in the benzene ring

1270 cm⁻¹ : stretching vibration of C--O of ester,

1000 to 1160 cm⁻¹ : stretching vibration of C--O--C of cellulose

680 to 900 cm⁻¹ : out-of-plane deformation vibration of benzene ring.

Substantially no absorption at around 3450 cm⁻¹ due to OH of cellulosewas observed. This fact suggested that the product substantiallycomprised a trisubstituted compound. In the proton NMR spectrumdetermined in CDCl₃, the characteristic absorptions were as follows:

6.9 to 8.3 ppm: proton of benzene ring, and

3.0 to 5.7 ppm: protons of the cellulose ring and methylene in position6.

The ratio of intensities of the absorptions was 27:7.

SYNTHESIS EXAMPLE 5 (Synthesis of cellulose tricinnamate)

70 ml of dehydrated pyridine, 7.7 ml of dehydrated triethylamine and 50milligrams of 4-dimethylaminopyridine were added to 1.5 grams of thecellulose obtained in Synthesis Example 2. 13.9 grams of cinnamoylchloride was added to the mixture under stirring and the reaction wascarried out at 100° C. for 5 hours. After cooling, the product was addedto 400 ml of ethanol under stirring to form precipitates. Afterfiltration through a glass filter, the product was washed thoroughlywith ethanol. After vacuum drying, the product was dissolved in 30 ml ofmethylene chloride. After removal of insoluble matter, the product wasreprecipitated from 400 ml of ethanol. The precipitates were filtered,washed with ethanol, dehydrated and dried to obtain 5.0 grams ofcellulose cinnamate. The product was dissolved in methylene chloride andthe solution was applied to a sodium chloride tablet and dried. Theinfrared absorption spectrum of the product had the followingcharacteristic absorption bands:

around 3050 cm⁻¹ : stretching vibration of olefinic C-H,

1730 cm⁻¹ : stretching vibration of C═O of carboxylic ester,

1640 cm^(-m) : stretching vibration of C═O,

1585, 1500, 1460 cm⁻¹ : skeletal vibration due to stretching of carbonand carbon in the benzene ring,

1250 cm⁻¹ : stretching vibration of C--O of ester,

1040 to 1160 cm⁻¹ : stretching vibration of C--O--C of cellulose,

990 cm⁻¹ : deformation vibration of olefinic C--H,

675 to 900 cm⁻¹ : out-of-plane deformation vibration of benzene ring.

Substantially no absorption at around 3450 cm⁻¹ due to OH of cellulosewas observed. This fact suggested that the product substantiallycomprised a trisubstituted compound. In the proton NMR spectrumdetermined in CDCl₃, the characteristic absorptions were as follows: 5.9to 7.8 ppm: proton of cinnamic acid segment, and

3.2 to 5.5 ppm: protons of the glucose ring of cellulose and methylenein position 6.

The ratio of intensities of these absorptions was 3:1.

SYNTHESIS EXAMPLE 6 (Synthesis of cellulose tri-β-naphthoate):

20 ml of pyridine and 5 ml of triethylamine were added to 1.0 grams ofthe cellulose obtained in Synthesis Example 2, 10.6 grams of β-naphthoylchloride (a product of Aldrich Co.) and 0.05 grams of4-dimethylaminopyridine (a product of Aldrich Co.). The mixture was keptat 80° C. for 2 hours and then at 100° C. for 4 hours. After cooling,the reaction liquid was added to methanol. Precipitates thus formed werefiltered, washed with methanol repeatedly and dried in vacuo to obtain3.85 grams of a product. The product was dissolved in dichloromethane.After filtration through a glass filter (G-3) to remove a small amountof insoluble matter, the product was purified by reprecipitation frommethanol. In the IR spectrum, characteristic absorptions were observedat 3060, 1735, 1280, 1230, 1200, 1140, 1100, 795 and 785 cm⁻¹ and nostretching vibration of a hydroxyl group at around 3500 cm⁻¹ wasobserved. This fact suggested that the product was a trisubstitutedcompound.

EXAMPLE 1

1.2 grams of cellulose tris-4-biphenylcarboxylate obtained in SynthesisExample 3 was dissolved in a mixture of 7.5 ml of dichloromethane and1.0 ml of benzene. After filtration through a glass filter (G3), about7.5 ml of the solution was absorbed by the silica beads obtained inSynthesis Example 1. The solvent was removed under reduced pressure toobtain a powdery, supported material.

EXAMPLE 2

1.2 grams of cellulose tris-p-phenylazobenzoate obtained in SynthesisExample 4 was dissolved in 7.5 grams of dichloromethane. 7.5 ml of thesolution was absorbed by the silica beads obtained in SynthesisExample 1. The solvent was distilled off under reduced pressure toobtain a powdery, supported material.

EXAMPLE 3

1.2 grams of cellulose tricinnamate obtained in Synthesis Example 5 wasdissolved in 7.5 ml of dichloromethane. 7.5 ml of the solution wasabsorbed by the silica beads obtained in Synthesis Example 1. Thesolvent was distilled off under reduced pressure to obtain a powdery,supported material.

EXAMPLE 4

1.1 g of cellulose tri-β-naphthoate obtained in Synthesis Example 6 wasdissolved in 6.9 ml of dichloromethane. 7.0 ml of the solution wasabsorbed by 3.10 grams of the silica beads obtained in SynthesisExample 1. The solvent was distilled off under reduced pressure toobtain a powdery, supported material.

APPLICATION EXAMPLE 1

The silica beads carrying cellulose tris-4-biphenylcarboxylate obtainedin Example 1 were packed in a stainless steel column having a length of25 cm and an inner diameter of 0.46 cm by slurry process. Thehigh-performance liquid chromatograph used was TRIROTAR-SR (a product ofJapan Spectroscopic Co., Ltd.) and the detector used was UVIDEC-V. Theresults of resolution of various racemic compounds are shown in Table 1.

                                      TABLE 1                                     __________________________________________________________________________                               Separation                                                                          Rate of                                                                             Flow                                                      Capacity ratio                                                                        factor                                                                              separation                                                                          rate                                   Racemates          k'.sub.1                                                                          k'.sub.2                                                                          α                                                                             Rs    ml/min                                 __________________________________________________________________________     ##STR10##         2.44                                                                              3.20                                                                              1.31  1.65  0.5                                     ##STR11##         2.74                                                                              5.04                                                                              1.84  1.39  0.5                                     ##STR12##         7.28                                                                              8.30                                                                              1.14  0.88  0.5                                     ##STR13##         4.28                                                                              4.96                                                                              1.16  0.64  0.5                                    __________________________________________________________________________     solvent: hexane/2propanol (9:1)                                          

APPLICATION EXAMPLE 2

The silica beads carrying cellulose trisazobenzenecarboxylate obtainedin Example 2 were packed in a stainless steel column having a length of25 cm and an inner diameter of 0.46 cm by slurry process. Thehigh-performance liquid chromatograph used was TRIROTAR-SR (a product ofJapan Spectroscopic Co., Ltd.) and the detector used was UVIDEC-V. Theresults of resolution of various racemic compounds are shown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________                               Separation                                                                          Rate of                                                                             Flow                                                      Capacity ratio                                                                        factor                                                                              separation                                                                          rate                                   Racemates          k'.sub.1                                                                          k'.sub.2                                                                          α                                                                             Rs    ml/min                                 __________________________________________________________________________     ##STR14##         1.45                                                                              1.85                                                                              1.28  1.36  0.5                                     ##STR15##         1.94                                                                              2.74                                                                              1.42  1.10  0.5                                     ##STR16##         4.44                                                                              5.10                                                                              1.15  0.84  0.5                                     ##STR17##         3.25                                                                              3.65                                                                              1.12  --    0.5                                    __________________________________________________________________________     solvent: hexane/2propanol (9:1)                                          

APPLICATION EXAMPLE 3

The silica beads carrying cellulose tricinnamate obtained in Example 3were packed in a stainless steel column having a length of 25 cm and aninner diameter of 0.46 cm by slurry process. The high-preformance liquidchromatograph used was TRIROTAR-SR (a product of Japan SpectroscopicCo., Ltd.) and the detector used was UVIDEC-V. The results of resolutionof various racemic compounds are shown in Table 3.

                                      TABLE 3                                     __________________________________________________________________________                               Separation                                                                          Rate of                                                                             Flow                                                      Capacity ratio                                                                        factor                                                                              separation                                                                          rate                                   Racemates          k'.sub.1                                                                          k'.sub.2                                                                          α                                                                             Rs    ml/min                                 __________________________________________________________________________     ##STR18##         2.75                                                                              3.17                                                                              1.15  1.14  0.5                                     ##STR19##         9.64                                                                              10.4                                                                              1.08  0.8   0.5                                     ##STR20##         5.28                                                                              8.04                                                                              1.52  0.7   0.5                                     ##STR21##         6.19                                                                              7.77                                                                              1.26  1.88  0.5                                     ##STR22##         4.64                                                                              13.1                                                                              2.82  3.46  0.5                                    __________________________________________________________________________     solvent: hexane/2propanol (9:1).                                         

APPLICATION EXAMPLE 4

The silica beads carrying cellulose tri-β-naphthoate obtained in Example4 were packed in a stainless steel column having a length of 25 cm andan inner diameter of 0.46 cm by the slurry process. The high-performanceliquid chromatograph used was TRIROTAR-SR (a product of JapanSpectroscopic Co., Ltd.) and the detector used was UVIDEC-V. The resultsof the resolution of trans-stilbene oxide are shown in Table 4.

                  TABLE 4                                                         ______________________________________                                                 Capacity                                                                              Separation                                                                              Rate of   Flow                                              ratio   factor    separation                                                                              rate                                     Racemates  k'.sub.1                                                                             k'.sub.2                                                                             α Rs      ml/min                               ______________________________________                                         ##STR23## 2.97   4.70   1.58    1.31    0.5                                  ______________________________________                                         solvent: hexane/2propanol (9:1).                                         

SYNTHESIS EXAMPLE 7 (Synthesis Example 7 (Synthesis of p-chlorocinnamoylchloride)

100 ml of benzene was added to 18.3 grams of p-chlorocinnamic acid. 12ml of thionyl chloride was added dropwise slowly thereto at ambienttemperature. The temperature was elevated to 80° C. and the heating wascontinued until foaming ceased. Benzene and thionyl chloride weredistilled off and the residue was dried thoroughly under reducedpressure.

SYNTHESIS EXAMPLE 8 (Synthesis of cellulose tris-p-chlorocinnamate)

1 gram of cellulose obtained in Synthesis Example 2 was dispersed in 50ml of pyridine. 11.2 grams of p-chlorocinnamoyl chloride was added tothe dispersion and the reaction was carried out at 90° C. for 5 hours.

After cooling, the reaction mixture was added to ethanol to formprecipitates, which were washed with ethanol and dried in vacuo. Thedried product was dissolved in methylene chloride. The solution wasfiltered through a glass filter (G-3). The filtrate was added to ethanolto form precipitates, which were washed thoroughly with ethanol anddried.

Cellulose p-chlorocinnamate thus obtained was dissolved in methylenechloride. The solution was applied to a rock salt cell and dried. In theIR absorption spectrum, substantially no absorption due to an OH groupof cellulose was observed.

SYNTHESIS EXAMPLE 9 (Synthesis of m-chlorocinnamoyl chloride)

100 ml of benzene was added to 18.3 grams of m-chlorocinnamic acid. 12ml of thionyl chloride was added dropwise slowly thereto at ambienttemperature. The temperature was elevated to 80° C. and the heating wascontinued until foaming ceased. Benzene and thionyl chloride weredistilled off and the residue was dried thoroughly under reducedpressure.

SYNTHESIS EXAMPLE 10 (Synthesis of cellulose tris-m-chlorocinnamate)

1 gram of cellulose obtained in Synthesis Example 2 was dispersed in 50ml of pyridine. A solution of 11.2 grams of m-chlorocinnamoyl chloridein 5 ml of benzene was added to the dispersion and the reaction wascarried out at 90° C for 5 hours.

After cooling, the reaction mixture was added to ethanol to formprecipitates, which were washed with ethanol and dried in vacuo. Thedried product was dissolved in methylene chloride. The solution wasfiltered through a glass filter (G-3). The filtrate was added to ethanolto form precipitates, which were washed thoroughly with ethanol anddried.

Cellulose m-chlorocinnamate thus obtained was dissolved in methylenechloride. The solution was applied to a rock salt cell and dried. In theIR absorption spectrum, substantially no absorption due to an OH groupof cellulose was observed.

SYNTHESIS EXAMPLE 11 Synthesis of p-methylcinnamoyl chloride)

100 ml of benzene was added to 16.2 grams of p-methylcinnamic acid. 12ml of thionyl chloride was added dropwise slowly thereto at ambienttemperature. The temperature was elevated to 70° C. and the heating wascontinued until foaming ceased. Benzene and thionyl chloride weredistilled off and the residue was dried thoroughly under reducedpressure.

SYNTHESIS EXAMPLE 12 (Synthesis of cellulose tris-p-methylcinnamate)

1 gram of the cellulose obtained in Synthesis Example 2 was dispersed in50 ml of pyridine. 10.1 grams of p-methylcinnamoyl chloride was added tothe dispersion and the reaction was carried out at 95° C. for 5 hours.

After cooling, the reaction mixture was added to ethanol to formprecipitates, which were washed with ethanol and dried in vacuo. Thedried product was dissolved in methylene chloride. The solution wasfiltered through a glass filter (G-3). The filtrate was added to ethanolto form precipitates, which were washed thoroughly with ethanol anddried.

Cellulose p-methylcinnamate thus obtained was dissolved in methylenechloride. The solution was applied to a rock salt cell and dried. In theIR absorption spectrum, substantially no absorption due to an OH groupof cellulose was observed.

SYNTHESIS EXAMPLE 13 (Synthesis of p-methoxycinnamoyl chloride)

100 ml of benzene was added to 17.8 grams of p-methoxycinnamic acid. 12ml of thionyl chloride was added dropwise slowly thereto at ambienttemperature. The temperature was elevated to 70° C. and the heating wascontinued until foaming ceased. Benzene and thionyl chloride weredistilled off and the residue was dried thoroughly under reducedpressure.

SYNTHESIS EXAMPLE 14 (Synthesis of cellulose tris-p-methoxycinnamate)

1 gram of cellulose obtained in Synthesis Example 2 was dispersed in 50ml of pyridine. 10.9 grams of p-methoxycinnamoyl chloride was added tothe dispersion and the reaction was carried out at 95° C. for 5 hours.

After cooling, the reaction mixture was added to ethanol to formprecipitates, which were washed with ethanol and dried in vacuo. Thedried product was dissolved in methylene chloride. The solution wasfiltered through a glass filter (G-3). The filtrate was added to ethanolto form precipitates, which were washed thoroughly with ethanol anddried.

Cellulose p-methoxycinnamate thus obtained was dissolved in methylenechloride. The solution was applied to a rock salt cell and dried. In theIR absorption spectrum, substantially no absorption due to an OH groupof cellulose was observed.

Example 15 Synthesis of α-cyanocinnamoyl chloride)

100 ml of benzene was added to 17.3 grams of α-cyanocinnamic acid. 12 mlof thionyl chloride was added dropwise slowly thereto at ambienttemperature. The temperature was elevated to 70° C. and the heating wascontinued until foaming ceased. Benzene and thionyl chloride weredistilled off and the residue was dried thoroughly under reducedpressure.

SYNTHESIS EXAMPLE 16 Synthesis of cellulose tris-α-cyanocinnamate)

1 gram of the cellulose obtained in Synthesis Example 2 was dispersed in50 ml of pyridine. 10.6 grams of α-cyanocinnamoyl chloride was added tothe dispersion and the reaction was carried out at 95° C. for 5 hours.

After cooling, the reaction mixture was added to ethanol to formprecipitates, which were washed with ethanol and dried in vacuo. Thedried product was dissolved in methylene chloride. The solution wasfiltered through a glass filter (G-3). The filtrate was added to ethanolto form precipitates, which were washed thoroughly with ethanol anddried.

Cellulose α-cyanocinnamate thus obtained was dissolved in methylenechloride. The solution was applied to a rock salt cell and dried. In theIR absorption spectrum, substantially no absorption due to an OH groupof cellulose was observed.

SYNTHESIS EXAMPLE 17 (Synthesis of 3-(2-thienyl)acryloylchloride)

65 ml of benzene was added to 10 grams of 3-(2-thienyl)acrylic acid. 7.8ml of thionyl chloride was added dropwise slowly thereto at ambienttemperature. The temperature was elevated to 70° C. and the heating wascontinued until foaming ceased. Benzene and thionyl chloride weredistilled off and the residue was dried thoroughly under reducedpressure.

SYNTHESIS EXAMPLE 18 (Synthesis of cellulose tris-3-(2-thienyl)acrylate)

1 gram of the cellulose obtained in Synthesis Example 2 was dispersed in50 ml of pyridine. 9.6 grams of 3-(2-thienyl)acryoyl chloride was addedto the dispersion and the reaction was carried out at 95° C. for 5hours.

After cooling, the reaction mixture was added to ethanol to formprecipitates, which were washed with ethanol and dried in vacuo. Thedried product was dissolved in methylene chloride. The solution wasfiltered through a glass filter (G-3). The filtrate was added to ethanolto form precipitates, which were washed thoroughly with ethanol anddried.

Cellulose 3-(2-thienyl)acrylate thus obtained was dissolved in methylenechloride. The solution was applied to a rock salt cell and dried. In theIR absorption spectrum, substantially nc absorption due to an OH groupof cellulose was observed.

SYNTHESIS EXAMPLE 19 (Synthesis of 3-(3-pyridyl)-acryloyl chloridehydrochloride)

67 ml of benzene was added to 10 grams of 3-(3-pyridyl)-acrylic acid.8.1 ml of thionyl chloride was added dropwise slowly thereto at ambienttemperature. The temperature was elevated to 70° C. and the heating wascontinued until foaming ceased. Benzene and thionyl chloride weredistilled off and the residue was dried thoroughly under reducedpressure.

SYNTHESIS EXAMPLE 20 (Synthesis of cellulose tris-3-(3-pyridyl)acrylate)

1 gram of the cellulose obtained in Synthesis Example 2 was dispersed in50 ml of pyridine. 11.3 grams of 3-(3-pyridyl)acryloyl chloridehydrochloride was added to the dispersion and the reaction was carriedout at 95° C. for 5 hours.

After cooling, the reaction mixture was added to ethanol to formprecipitates, which were washed with ethanol and dried in vacuo. Thedried product was dissolved in methylene chloride. The solution wasfiltered through a glass filter (G-3). The filtrate was added to ethanolto form precipitates, which were washed thoroughly with ethanol anddried.

Cellulose 3-(3-pyridyl)acrylate thus obtained was dissolved in methylenechloride. The solution was applied to a rock salt cell and dried. In theIR absorption spectrum, substantially no absorption due to an OH groupof cellulose was observed.

SYNTHESIS EXAMPLE 21 (Synthesis of amylose tricinnamate)

1.8 grams of Amylose DEX-III (a product of Hayashibara Biochem. Lab.Inc.) (degree of polymerization: 100) was added to 10 ml of water. Twodrops of a 0.1N aqueous NaOH solution and two drops of ethanol wereadded to the mixture. The mixture was heated to 50° C. for 30 min,neutralized with acetic acid and added to ethanol to form precipitates,which were washed with ethanol and dried in vacuo.

1.5 grams of the dried amylose was dispersed in a mixture of 70 ml ofpyridine, 7.7 ml of triethylamine and 50 milligrams of4-dimethylaminopyridine. 13.9 grams of cinnamoyl chloride was added tothe dispersion and the reaction was carried out at 95 to 100° C. for 5hours. After cooling, the reaction mixture was added to ethanol to formprecipitates, which were washed with ethanol and dried. The dried samplewas dissolved in methylene chloride. The solution was filtered through aglass filter (G-3). The filtrate was added to ethanol to formprecipitates, which were washed with ethanol and dried in vacuo.

The dried amylose cinnamate was dissolved in methylene chloride. Thesolution was applied to a rock salt cell and dried. In IR absorptionspectrum, substantially no absorption due to an OH group of cellulosewas observed.

Examples 5, 6, 7, 8, 9, 10, 11 and 12

1.2 grams of each of the polysaccharide ester derivatives obtained inSynthesis Examples 8, 10, 12, 14, 16, 18, 20 and 21 was dissolved in 7.5ml of dichloromethane. The solution was filtered through a glass filter(G-3) and the filtrate was mixed thoroughly with 3.5 grams of the silicabeads obtained in Synthesis Example 1 (the amount of the silica beadsbeing 3.0 grams in Example 12). Dichloromethane was distilled off underreduced pressure to obtain a powdery, supported material.

Application Examples 5, 6, 7, 8, 9, 10, 11 and 12

Each of the supported material obtained in Examples 5, 6, 7, 8, 9, 10,11 and 12 was packed in a column in the same manner as in ApplicationExample 1. The optical resolution was conducted by liquid chromatographywith the obtained column. The optically resolved compounds andseparation factors α of the optical isomers of them are shown in Table6. The eluent used in the resolution was a mixture of hexane and2-propanol (9:1), the flow rate was 0.5 ml/min and the analysistemperature was 20° to 25° C.

                  TABLE 5                                                         ______________________________________                                        Polysaccharide derivative                                                     Example Compound             Synthesis Ex.                                    ______________________________________                                        5       cellulose tis-p-chlorocinnamate                                                                     8                                               6       cellulose tris-m-chlorocinnamate                                                                   10                                               7       cellulose tris-p-methylcinnamate                                                                   12                                               8       cellulose tris-p-methoxycinnamate                                                                  14                                               9       cellulose tris-α-cyanocinnamate                                                              16                                                10     cellulose tris-3-(2-thienyl)acrylate                                                               18                                                11     cellulose tris-3-(3-pyridyl)acrylate                                                               20                                                12     amylose tricinnamate 21                                               ______________________________________                                    

                                      TABLE 6                                     __________________________________________________________________________    Application                                                                         Resolving agent                                                         Example                                                                             Effective component                                                                           Ex.                                                                              Compound   α                                   __________________________________________________________________________    5     cellulose tris-p-chlorocinnamate                                                              5  benzoin    1.11                                                               mandelamide                                                                              1.06                                      6     cellulose tris-m-chlorocinnamate                                                              6  t-stilbene oxide                                                                         1.12                                      7     cellulose tris-p-methylcinnamate                                                              7  Troger's base                                                                            1.78                                      8     cellulose tris-p-methoxycinnamate                                                             8  Troger's base                                                                            3.63                                                               benzoin    1.17                                                               ethotoin*  1.23                                      9     cellulose tris-α-cyanocinnamate                                                         9  t-stilbene oxide                                                                         1.14                                      10    cellulose tris-3-(2-thienyl)-                                                                 10 Troger's base                                                                            2.41                                            acrylate                                                                11    cellulose tris-3-(3-pyridyl)-                                                                 11 Troger's base                                                                            1.54                                            acrylate           methyl α-[4-(4'-                                                                   1.12                                                               fluorophenoxy)                                                                phenoxy]propionate**                                 __________________________________________________________________________     *Structure of ethotoin:                                                       ##STR24##                                                                     **Structure of methyl α-[4(4'-fluorophenoxy)phenoxy]-propionate:        ##STR25##                                                                

SYNTHESIS EXAMPLE 22 (Synthesis of curdlan tricinnamate)

4 grams of curdlan triacetate was suspended in 9 ml of 2-propanol and,after adding 3.0 ml of 100% hydrazine hydrate, the mixture was kept at70° C. for 4.5 hours. The formed curdlan was filtered, washed with2-propanol twice and then with acetone three times and dried.

1.5 grams of the obtained curdlan was dispersed in a mixture of 70 ml ofpyridine, 7.7 ml of triethylamine, and 50 milligrams of4-dimethylamino-pyridine and, after adding 13.9 grams of cinnamoylchloride, the mixture was reacted at 100° C. for 5 hours. After cooling,the reaction mixture was poured into ethanol to precipitate curdlancinnamate. The precipitate was washed with ethanol, dried and dissolvedin methylene chloride. The solution was filtered through a glass filter(G-3) and poured into ethanol. The formed precipitate was washed wellwith ethanol and dried in vacuo. The dried sample was dissolved inmethylene chloride, and the solution was applied to a rock salt cell anddried. The infrared absorption spectrum of the curdlan cinnamate showedhardly any absorption assigned to unreacted OH.

EXAMPLE 13

1.2 grams of the curdlan cinnamate obtained in Synthesis Example 22 wasdissolved in 7.5 ml of dichloromethane and after filtering the solutionthrough a glass filter (G-3), the filtrate was mixed with 3.5 grams ofthe silica beads obtained in Synthesis Example 1. The solvent wasdistilled off in vacuo to obtain a powdery supported resolving agent.APPLICATION EXAMPLE 13

When (±) benzoin was optically resolved in the same way as inApplication Example 1 by using the supported agent obtained in Example13, the magnitude of the separation factor (c), 1.22 was attained andthe dextrorotatory enantiomer eluted first (eluent: hexane and2-propanol at 9:1).

SYNTHESIS EXAMPLE 23 (Synthesis of cellulosetris(4-styrylphenylcarbamate))

20.45 grams of p-nitrophenylacetic acid, 12.21 grams of benzaldehyde and4.6 ml of piperidine were placed in a 100-ml short-neck Kjeldahl flask.An Allihn condenser was attached to the flask and the flask was placedin a oil bath to conduct the reaction at 155° C. for 7 hours. The liquidwhich was yellow in the initial stage of the reaction turned black inthe final stage. The liquid was converted into black crystals when thetemperature was lowered to room temperature. The 4-nitrostilbene productwas thoroughly washed with acetic acid, filtered through a glass filter,dried in a vacuum line in a desiccator for 3 hours and dried in vacuo at60° C. for 2 hours.

330 ml of acetic acid and 87.95 grams of tin(II) chloride were placed ina 1-1 three-necked flask. Hydrogen chloride was introduced thereinto for2 hours. When the turbidity of the solution was reduced, 14.53 grams of4-nitrostilbene prepared in the above-described step was added thereto.Immediately a violent exothermic reaction occurred and the milkysolution was converted into a light green turbid solution. The reactionwas continued for additional about one hour and the reaction mixture wasleft to stand overnight. The solution had an upper yellow liquid layerand a lower layer having green precipitates. The product was heated at100° C. in an oil bath for about 1.5 hours, filtered through a Buchnerfunnel, dried in a vacuum line in a desiccator for 2 hours and thendried in vacuo at 60° C. for 2 hours. After drying, 1 liter of a 3mol/liter aqueous KOH solution was added thereto and the mixture washeated at 100° C. in an oil bath. Cream-colored fluffy precipitates thusformed were separated by filtration through a glass filter, thoroughlywashed with an aqueous KOH solution and pure water and then dissolved indiethyl ether. The liquid layer was dried over calcium chloride. Thesolvent was removed with an evaporator. The 4-aminostilbene product wasrecrystallized from ethanol, dried in a vacuum line in a desiccator for2 hours and dried in vacuo at 60° C. for 2 hours.

200 ml of toluene was placed in a 1-liter three-necked flask. Phosgeneformed by adding fuming sulfuric acid to carbon tetrachloride understirring and under reflux of carbon tetrachloride was introducedthereinto. After the inside of the flask was thoroughly purged withphosgene, a solution of 8.26 grams of 4-aminostilbene prepared in theabove step in 300 ml of toluene was added dropwise thereto and thetemperature was gradually elevated to conduct the reaction under refluxof toluene. The reaction time was 4 hours. Phosgene was introducedthereinto for additional about 30 minutes and then nitrogen wasintroduced thereinto for about 1 hour. The reaction solution was yellowand clear. Toluene was removed by atmospheric distillation followed byvacuum distillation (38 mmHg, 35° C.) to give cream-colored crystals of4-aminostilbene.

0.60 grams of cellulose and 50 ml of pyridine were placed in a 100-mlshort-neck Kjeldahl flask and about 20 ml of pyridine was distilled offunder atmospheric pressure. 3.76 grams of 4-aminostyrylphenyl isocyanateprepared in the above step was added thereto. An Allihn condenserequipped with a calcium chloride tube was attached thereto and thereaction was conducted at 100° C. in an oil bath for 21 hours. Thereaction solution was poured into methanol and the crystals thus formedwere separated by filtration through a glass filter, dried in a vacuumline in a desiccator and dried in vacuo at 50° C. for 2 hours to yieldcellulose tris(4-styrylphenylcarbamate).

SYNTHESIS EXAMPLE 24 (Synthesis of cellulosetris(4-biphenylylcarbamate))

About 200 ml of toluene was placed in a 1-liter three-necked flask andphosgene was introduced thereinto under cooling. A solution of 25 gramsof 4-aminobiphenyl in 200 ml of toluene was added dropwise thereto. Thetemperature was gradually elevated and the reaction was conducted undera reflux of toluene for 2 hours. The reaction liquid turned reddishpurple. The toluene was removed by atmospheric distillation followed byvacuum distillation (38 mmHg, 31° C.). The liquid was red and turnedinto a gray solid at room temperature. The grey solid was 4-biphenylylisocyanate.

60 ml of pyridine and 0.72 grams of cellulose were placed in a 100-mlshort-neck Kjeldahl flask and an Allihn condenser equipped with acalcium chloride tube was attached thereto. After stirring at 100° C. inan oil bath for 14 hours, about 30 ml of pyridine was distilled offunder atmospheric pressure. 3.92 grams of 4-biphenylyl isocyanate wasadded thereto and the mixture was reacted at 100° C. in the oil bath for18 hours. The reaction solution was poured into methanol and thecellulose tris(4-biphenylylcarbamate) product thus precipitated wasseparated by filtration through a glass filter, dried in a vacuum linein a desiccator for 2 hours and dried in vacuo at 50° C. for 2 hours.

SYNTHESIS EXAMPLE 25 (Synthesis of amylosetris(4-styrylphenylcarbamate))

60 ml of pyridine and 0.62 grams of amylose were placed in a 100-mlshort-necked Kjeldahl flask and an Allihn condenser equipped with acalcium chloride tube was attached thereto. After stirring at 100° C. inan oil bath for 12 hours, about 30 ml of pyridine was distilled offunder atmospheric pressure. 3.78 grams of 4-aminostilbene was addedthereto and the mixture reacted at 100° C. in the oil bath for 24 hours.The reaction solution was poured into methanol and the product thusprecipitated was separated by filtration through a glass filter, driedin a vacuum line in a desiccator for 2 hours and then dried in vacuo at40° C. for 2 hours.

SYNTHESIS EXAMPLE 26 (Synthesis of amylose tris(4-biphenylylcarbamate))

60 ml of pyridine and 0.72 grams of amylose were placed in a 100 mlshort-necked Kjeldahl flask and an Allihn condenser equipped with acalcium chloride tube was attached thereto. After stirring at 100° C. inan oil bath for 13 hours, about 30 ml of pyridine was distilled offunder atmospheric pressure. 3.90 grams of 4-biphenylyl isocyanate wasadded thereto and the mixture was subjected to the reaction at 100° C.in the oil bath for 20 hours. The reaction solution was poured intomethanol and the amylose tris(4-biphenylylcarbamate) product thusprecipitated was separated by filtration through a glass filter, driedin a vacuum line in a desiccator for 2 hours and then dried in vacuo at50° C. for 3 hours.

The results of the elemental analysis of the triphenylcarbamatederivatives of Synthesis Examples 23-26 are shown in Table 7. It isapparent from this table that the analytical values were substantiallyequal to the calculated ones and, therefore, the hydroxyl groups of thecellulose or amylose has been replaced with the carbamate groups almostquantitatively. In the IR spectra, an absorption due to the stretchingvibration of NH of the carbamate group was observed at around 3300 cm⁻¹and that due to the stretching vibration of C═O was observed at around1750 cm⁻¹ to prove that the reaction has been completed.

                  TABLE 7                                                         ______________________________________                                        Analytical Data of Triphenylcarbamate Derivatives                             elemental analysis.sup.a                                                                 C %   H %      N %    [α].sub.D.sup.25                       ______________________________________                                        cellulose tris-                                                                            73.47   5.45     4.93 +58.9.sup.c                                (4-styrylphenyl-                                                                           (74.18  5.21     5.09                                            carbamate)                                                                    cellulose tris-                                                                            71.45   5.10     5.53 -16.1.sup.b                                (4-biphenylyl-                                                                             (71.29  4.95     5.62                                            carbamate)                                                                    amylose tris-                                                                              73.76   5.35     5.09 -409.sup.c                                 (4-styrylphenyl-                                                                           (74.18  5.21     5.09                                            carbamate)                                                                    amylose tris-                                                                              71.48   5.07     5.54 -266.sup.b                                 (4-biphenylyl                                                                              (72.29  4.95     5.62                                            carbamate)                                                                    ______________________________________                                         .sup.a calculated values of elemental analysis are shown in parentheses       .sup.b in tetrahydrofuran                                                     .sup.c in N,Ndimethylacetamide                                           

SYNTHESIS EXAMPLE 27 (Synthesis of cellulosetris[4-2-phenylethynyl)phenylcarbamate])

An Allihn condenser was attached to a 500-ml three-necked flask and theinside of the flask was purged with nitrogen. 80-ml of Et₂ NH, 15.2milligrams (6.79×10⁻⁵ mol) of Pd(CH₃ CO₂)₂, 33.7 milligrams (1.24×10⁻⁴mol) of P(Ph)₃, 9.96 grams (49.3 mmol) of ##STR26## and 8.37 grams (81.9mmol) of ##STR27## were placed therein and the flask was heated in anoil bath in a nitrogen atmosphere. The reaction solution was black andbubbled violently at a bath temperature of around 90° C. to increase theviscosity thereof. The reaction was conducted at 100° C. for 4 hours.

The three-necked flask was cooled in ice and 200ml of 3N HCl was slowlyadded thereto. Brown precipitates thus formed were separated byfiltration and subjected to extraction with a mixture of about 170-ml ofbenzene with 50-ml of water by means of a 500-ml separatory funneltwice. The solvent was removed from the benzene layer by evaporation andthe residue was dried at a constant temperature of 50° C. for 2 hours.After recrystallization from 137-ml of ethanol/water (5:2), thenitrotolan product was dried at a constant temperature of 50° C. for 2hours.

34.5 g of Zn powder and a solution of 5.88 grams of nitrotolan in 760-mlof EtOH were placed in a 1-liter short-neck Kjeldahl flask and an Allihncondenser was attached thereto. 136 grams of a concentrated aqueous HClsolution (35%) was added dropwise thereto over 1.5 hours and the mixturewas stirred for 2.5 hours. A precipitate thus formed was separated byfiltration and an aqueous KOH solution was added to the filtrate untilthe pH was increased to about 10. A precipitate thus formed wassubjected to the extraction with 300-ml of benzene and 50-ml of watertwice. The benzene layer was dried over Na₂ SO₄ overnight. The solventwas removed by evaporation. After filtration through a glass filter, thep-aminotolan product was dried at a constant temperature of 40° C. for 3hours.

11.06 grams of p-aminotolan was dissolved in 300ml of toluene.Separately, 100-ml of fuming sulfuric acid was added dropwise slowly to205-ml of carbon tetrachloride under reflux to form phosgene. After theinside of the reactor had been sufficiently purged with phosgene, thesolution of p-aminotolan in toluene was added dropwise thereto. Thetemperature was slowly elevated to conduct the reaction under a refluxof toluene. The reaction time was 4 hours. After the completion of thereaction, a major part of the toluene was distilled off underatmospheric pressure. Then toluene was removed by vacuum distillation at28.5° C. under 20 mmHg. The isocyanate could not be distilled off andbrown crystals remained.

0.74 grams of cellulose was stirred in 80-ml of pyridine at 100° C. for1 hour. About 40-ml of pyridine was distilled off. 4.53 grams of theisocyanate was added to the residue and the reaction was conducted at100° C. for 17 hours. The reaction mixture was poured into methanol toform a precipitate. After stirring for 2 hours, the mixture was filteredthrough a glass filter. The cellulosetris[4-(2-phenylethynyl)phenylcarbamate]product was dried at a constanttemperature of 50° C. for 2 hours.

The results of the elemental analysis of the cellulosetris[4-(2-phenylethynylphenylcarbamate)] of Synthesis Example 27 areshown in Table 8. It is apparent from this table that the analyticalvalues were substantially equal to the calculated values and, therefore,the hydroxyl groups of the cellulose had been replaced with thecarbamate groups almost quantitatively.

                  TABLE 8                                                         ______________________________________                                        Elemental Analysis of Cellulose Tris[4-(2-phenyl-                             ethynylphenylcarbamate)]                                                                 C         H      N%                                                ______________________________________                                        Found        74.05       4.65   5.07                                          Calculated   74.71       4.55   5.12                                          [α].sub.D.sup.25 = +35.59°.                                      ______________________________________                                    

SYNTHESIS EXAMPLE 28 (Synthesis of cellulosetris(4-phenoxyphenyl-carbamate))

25 grams of commercially available 4-phenoxyaniline was dissolved in 700ml of toluene. A supernatant liquid thus formed was separated bydecantation and used in the reaction.

100 ml of fuming sulfuric acid was added slowly and dropwise to 270 mlof carbon tetrachloride under reflux and stirring to form phosgene.After the inside of the device was thoroughly purged with phosgene, asolution of 4-phenoxyaniline in toluene was added dropwise thereto andthe temperature was gradually elevated. The reaction was conducted undera reflux of toluene for 4 hours.

After the completion of the reaction, a major part of the toluene wasdistilled off under atmospheric pressure and then 4-phenoxyphenylisocyanate was distilled off at 120° C. under reduced pressure of 0.358mmHg. The isocyanate was in the form of a transparent liquid.

0.75 grams of cellulose was stirred in 60 ml of pyridine at 100° C. for1 hour. Then about 30 ml of pyridine was distilled off under atmosphericpressure. 4.43 grams of 4-phenoxyphenyl isocyanate was added thereto andthe reaction was conducted at 100° C. for 18 hours. The reaction mixturewas poured into 300 ml of methanol to form a white precipitate. Afterstirring for about 1 hour, the mixture was filtered through a glassfilter. The cellulose tris(4-phenoxyphenylcarbamate) product was driedin a vacuum line in a desiccator for 1.5 hours and then at a constanttemperature of 50° C. for 2 hours.

    ______________________________________                                        Elemental analysis:                                                                    C %         H %    N %                                               ______________________________________                                        Found      66.75         4.71   5.20                                          Calculated 67.91         4.69   5.28                                          ______________________________________                                    

SYNTHESIS EXAMPLE 29 (Synthesis of amylosetris(4-phenoxyphenylcarbamate))

0.77 grams of amylose was stirred in 65 ml of pyridine at 100° C. for 4hours. Then about 30 ml of pyridine was distilled off under atmosphericpressure. 4.53 grams of 4-phenoxyphenyl isocyanate was added thereto andthe reaction was conducted at 100° C. for 24 hours. The reaction mixturewas poured into 300 ml of methanol to form a white precipitate. Afterstirring for several hours, the mixture was filtered through a glassfilter. The product was dried in a vacuum line in a desiccator for 1hour and then at a constant temperature of 60° C. for about 2 hours. Theelemental analysis of the amylose tris(4-phenoxyphenylcarbamate) isshown in Table 9. The closeness of the numbers between the analyticalvalues and the calculated values indicate that the hydroxy groups of theamylose have been replaced with the carbamate groups almostquantitatively.

                  TABLE 9                                                         ______________________________________                                                 C %         H %    N %                                               ______________________________________                                        Found      66.40         4.68   5.18                                          Calculated 67.91         4.69   5.28                                          ______________________________________                                    

SYNTHESIS EXAMPLE 29 (Surface treatment of silica gel)

30 grams of silica gel (Lichrospher Si 4000) was dried in vacuo ataround 180° C. for 2 hours. 180 ml of benzene was dried by simpledistillation over metallic sodium, 6 ml of γ-aminopropyltriethoxysilaneand 1.8 ml of pyridine were added thereto and the mixture was heatedunder reflux in a nitrogen stream for 16 hours. The reaction mixture waspoured into methanol, filtered through a glass filter and dried.

EXAMPLE 14

The cellulose or amylose triphenyl derivatives of Synthesis Examples23-26 were dissolved in about 15 ml of N,N-dimethylacetamide. About 3 mlof the solution was added to the surface-treated silica gel having alarge pore diameter and shaken well to uniformly wet the silica gel,which was dried in vacuo at about 60° C. This operation was repeated tocause the silica gel to support the polymer.

The packing material prepared in the above step was subjected toparticle size classification with hexane/2-propanol (90:10). It was thenpacked in a stainless steel column having a length of 25 cm and an innerdiameter of 0.46 cm by the slurry packing method.

JASCO TRIROTOR-II was used in HPLC. The detector and polarimeter usedwere UV (JASCO UV DIC-100-III) and JASCO DIP-181C, respectively. Theoptical activity was determined with a flow cell having a size of 5cm×0.2 cm. The eluents used were hexane/2-propanol (IPA) (90/10),hexane/IPA/chloroform (90/5/5), hexane/IPA/chloroform (85/5/10),hexane/IPA/chloroform (75/5/20) and hexane/IPA/chloroform (78/2/20). Theflow rate and temperature were 0.5 ml/min and 25° C., respectively.

The following six racemic compounds were used in the optical resolution:benzoin (5), transstilbene oxide (6), 6,6'-dimethyl-2,2'-biphenyldiol(7e), transcyclopropanedicarboxylic dianilide (8),1,2,2,2tetraphenylethanol (9) and Troger's base (10). ##STR28##

The separation factors α on the cellulose and amylose triphenylcarbamatederivatives and cellulose and amlose triphenylcarbamates obtained whenhexane/2-propanol (90:10) was used as the eluent are shown in Table 10.

Cellulose tris(4-biphenylylcarbamate) behaved as a liquid crystal inTHF. Although other triphenylcarbamate derivatives did not behave as aliquid crystal, they were crystalline.

    TABLE 10      ##STR29##      ##STR30##      Separation factors (α) on cellulose and amylose triphenylcarbamate      derivatives Cellulose derivatives Amylose derivatives         CompoundsR     acemic      ##STR31##      ##STR32##      H      ##STR33##      ##STR34##      H               5      ##STR35##      1.05 1 1 1.20 1.23 1      6     ##STR36##      1.31 1.35 1.65 1.13 1.35 1.53      8     ##STR37##      1 1.31 1.45 2.53 2.48 1.52      9     ##STR38##      1 1.20 1.22 1.31 1.49 1.84  10      ##STR39##      1.19 1.25 1.37 1.09 1.12 1.2     Eluent, hexan2-propanol (90:10)

The compounds 1 to 4 had a poor solubility in solvents and were scarcelysoluble also in chloroform. Chloroform was added to the eluent to varythe composition thereof in the optical resolution, The results of usingcellulose tris(4-styrylphenylcarbamate), cellulosetris(4-biphenylylcarbamate), amylose tris(4-styrylphenylcarbamate) andamylose tris(4-biphenylylcarbamate) as separating agents for theabove-mentioned six racemic compounds are shown in Tables 11-14respectively. FIG. 1 shows the chromatographic resolution oftranscyclopropane dicarboxylic acid on a column using an amylosetris(4-styrylphenylcarbamate packing.

                  TABLE 11                                                        ______________________________________                                        Cellulose tris (4-styrylphenylcarbamate)                                      ______________________________________                                                 Racemic   Racemic                                                             Compound 5                                                                              Compound 6                                                            kl       α                                                                              kl     α                                                                            Rs                                     ______________________________________                                        Hex:IPA 90:10                                                                            3.54(+)  1.05   0.70(+)                                                                              1.22 0.88                                   Hex:IPA:CHCl.sub.3                                                                       3.11(+)  ˜1                                                                             0.59(+)                                                                              1.20 0.76                                   90:5:5                                                                        Hex:IPA:CHCl.sub.3                                                                       2.39(+)  ˜1                                                                             0.46(+)                                                                              1.21 0.77                                   85:5:10                                                                       Hex:IPA:CHCl.sub.3                                                                       1.31(+)  ˜1                                                                             0.58(+)                                                                              1.11                                        75:5:20                                                                       Hex:IPA:CHCl.sub.3                                                                       2.00(+)  ˜1                                                                             0.31(+)                                                                              1.23                                        78:2:20                                                                       ______________________________________                                                 Racemic      Racemic                                                          Compound 7   Compound 8                                                         kl       α                                                                              Rs   kl     α                                                                            Rs                                ______________________________________                                        Hex:IPA 90:10                                                                            1.13(-)  1.31   0.94 1.73(-)                                                                              ˜1                               Hex:IPA:CHCl.sub.3                                                                       1.63(-)  1.26   0.80 3.49(-)                                                                              1.13                                   90:5:5                                                                        Hex:IPA:CHCl.sub.3                                                                       1.25(-)  1.25   0.71 2.60(-)                                                                              1.26                                   85:5:10                                                                       Hex:IPA:CHCl.sub.3                                                                       0.91(-)  1.20   0.72 2.34(-)                                                                              1.22 0.59                              75:5:20                                                                       Hex:IPA:CHCl.sub.3                                                                       2.07(-)  1.13   0.47 11.00(-)                                                                             1.24                                   78:2:20                                                                       ______________________________________                                                 Racemic      Racemic                                                          Compound 9   Compound 10                                                        kl       α                                                                              Rs   kl     α                                                                            R                                 ______________________________________                                        Hex:IPA 90:10                                                                            1.23(+)  ˜1    1.17(+)                                                                              1.19 0.66                              Hex:IPA:CHCl.sub.3                                                                       1.16(+)  1.12        1.02(+)                                                                              1.22 0.80                              90:5:5                                                                        Hex:IPA:CHCl.sub.3                                                            85:5:10    0.87(+)  1.17        0.65(+)                                                                              1.24 0.75                              Hex:IPA:CHCl.sub.3                                                                       0.49(+)  1.19        0.37(+)                                                                              1.25                                   75:5:20                                                                       Hex:IPA:CHCl.sub.3                                                                       0.76(+)  1.25   0.81 2.74(+)                                                                              1.20 1.07                              78:2:20                                                                       ______________________________________                                    

                  TABLE 12                                                        ______________________________________                                        Cellulose tris (4-biphenylylcarbamate)                                        ______________________________________                                                 Racemic      Racemic                                                          Compound 5   Compound 6                                                         kl       α                                                                              Rs   kl     α                                                                            Rs                                ______________________________________                                        Hex:IPA 90:10                                                                            4.88(-)  ˜1    0.72(+)                                                                              1.41 1.23                              Hex:IPA:CHCl.sub.3                                                                       4.71(-)  ˜1    0.52(+)                                                                              1.40 1.29                              90:5:5                                                                        Hex:IPA:CHCl.sub.3                                                                       3.18(-)  ˜1    0.44(+)                                                                              1.34 1.03                              85:5:10                                                                       Hex:IPA:CHCl.sub.3                                                                       1.51(-)  ˜1    0.58(+)                                                                              1.17                                   75:5:20                                                                       Hex:IPA:CHCl.sub.3                                                                       2.78(-)  ˜1    0.32(+)                                                                              1.37 0.96                              78:2:20                                                                       ______________________________________                                                 Racemic      Racemic                                                          Compound 7   Compound 8                                                         kl       α                                                                              Rs   kl     α                                                                            Rs                                ______________________________________                                        Hex:IPA 90:10                                                                            1.38(-)  1.35   0.95 1.90(-)                                                                              1.31                                   Hex:IPA:CHCl.sub.3                                                                       1.96(-)  1.25   0.63 4.34(-)                                                                              1.56 1.47                              90:5:5                                                                        Hex:IPA:CHCl.sub.3                                                                       1.74(-)  1.21   0.74 3.52(-)                                                                              1.63 1.52                              85:5:10                                                                       Hex:IPA:CHCl.sub.3                                                                       1.02(-)  1.17   0.62 1.94(-)                                                                              1.86 2.00                              75:5:20                                                                       Hex:IPA:CHCl3                                                                            2.16(-)  1.12        11.40(-)                                                                             --   --                                78:2:20                    (not eluted)                                       ______________________________________                                                 Racemic      Racemic                                                          Compound 9   Compound 10                                                         kl      α                                                                              Rs   kl     α                                                                            Rs                                ______________________________________                                        Hex:IPA 90:10                                                                            1.67(+)  1.20        1.59(+)                                                                              1.25 0.67                              Hex:IPA:CHCl.sub.3                                                                       1.71(+)  1.41   1.29 1.12(+)                                                                              1.26 0.79                              90:5:5                                                                        Hex:IPA:CHCl.sub.3                                                                       1.18(+)  1.18   0.54 0.75(+)                                                                              1.28 0.82                              85:5:10                                                                       Hex:IPA:CHCl.sub.3                                                                       0.59(+)  1.48   1.16 0.34(+)                                                                              1.33                                   75:5:20                                                                       Hex:IPA:CHCl.sub.3                                                                       1.01(+)  1.55   1.40 0.69(+)                                                                              1.35                                   78:2:20                                                                       ______________________________________                                    

                  TABLE 13                                                        ______________________________________                                        Amylose tris (4-styrylphenylcarbamate)                                        ______________________________________                                                 Racemic      Racemic                                                          Compound 5   Compound 6                                                         kl       α                                                                              Rs   kl     α                                                                            Rs                                ______________________________________                                        Hex:IPA 90:10                                                                            4.06(+)  1.20   0.95 0.83(+)                                                                              1.19 0.83                              Hex:IPA:CHCl.sub.3                                                                       4.16(+)  1.19   0.92 0.71(+)                                                                              1.24 0.88                              90:5:5                                                                        Hex:IPA:CHCl.sub.3                                                                       2.77(+)  1.20   1.09 0.51(+)                                                                              1.25 0.76                              85:5:10                                                                       Hex:IPA:CHCl.sub.3                                                                       1.47(+)  1.19   1.08 0.35(+)                                                                              1.32 1.17                              75:5:20                                                                       Hex:IPA:CHCl.sub.3                                                                       1.65(+)  1.19   1.07 0.36(+)                                                                              1.31 0.67                              78:2:20                                                                       ______________________________________                                                 Racemic      Racemic                                                          Compound 7   Compound 8                                                         kl       α                                                                              Rs   kl     α                                                                            Rs                                ______________________________________                                        Hex:IPA 90:10                                                                            1.27(-)  1.13        1.31(+)                                                                              2.53 1.26                              Hex:IPA:CHCl.sub.3                                                                       2.02(-)  1.16   0.51 2.67(+)                                                                              3.27 1.90                              90:5:5                                                                        Hex:IPA:CHCl.sub.3                                                                       1.72(-)  1.17   0.62 2.19(+)                                                                              3.29 2.28                              85:5:10                                                                       Hex:IPA:CHCl.sub.3                                                                       1.12(-)  1.29   0.99 1.57(+)                                                                              3.44 3.06                              75:5:20                                                                       Hex:IPA:CHCl.sub.3                                                                       2.32(-)  1.24   0.82 5.12(+)                                                                              --   --                                78:2:20                    (not eluted)                                       ______________________________________                                                 Racemic      Racemic                                                          Compound 9   Compound 10                                                        kl        α                                                                             Rs   kl     α                                                                            Rs                                ______________________________________                                        Hex:IPA 90:10                                                                            1.69(+)  1.31   0.60 1.54(+)                                                                              1.09                                   Hex:IPA:CHCl.sub.3                                                                       1.75(+)  1.37   0.77 1.30(+)                                                                              1.11                                   90:5:5                                                                        Hex:IPA:CHCl.sub.3                                                                       1.28(+)  1.43   1.24 0.83(+)                                                                              1.15                                   85:5:10                                                                       Hex:IPA:CHCl.sub.3                                                                       0.80(+)  1.54   1.84 0.44(+)                                                                              1.19                                   75:5:20                                                                       Hex:IPA:CHCl.sub.3                                                                       1.03(+)  1.54   1.91 0.52(+)                                                                              1.23 0.69                              78:2:20                                                                       ______________________________________                                    

                  TABLE 14                                                        ______________________________________                                        Amylose tris (4-biphenylylcarbamate)                                          ______________________________________                                                 Racemic      Racemic                                                          Compound 5   Compound 6                                                         kl       α                                                                              Rs   kl     α                                                                            Rs                                ______________________________________                                        Hex:IPA 90:10                                                                            4.97(+)  1.23   1.42 0.78(+)                                                                              1.30 1.00                              Hex:IPA:CHCl.sub.3                                                                       5.12(+)  1.33   2.13 0.75(+)                                                                              1.31 1.37                              90:5:5                                                                        Hex:IPA:CHCl.sub.3                                                                       3.30(+)  1.30   2.05 0.53(+)                                                                              1.33 1.28                              85:5:5                                                                        Hex:IPA:CHCl.sub.3                                                                       1.75(+)  1.27   1.77 0.31(+)                                                                              1.36 0.90                              75:5:20                                                                       Hex:IPA:CHCl.sub.3                                                                       2.70(+)  1.29   2.05 0.41(+)                                                                              1.43 1.30                              78:2:20                                                                       ______________________________________                                                 Racemic      Racemic                                                          Compound 7   Compound 8                                                         kl       α                                                                              Rs   kl     α                                                                            Rs                                ______________________________________                                        Hex:IPA 90:10                                                                            1.63(-)  1.35   0.93 1.46(+)                                                                              2.48 1.84                              Hex:IPA:CHCl.sub.3                                                                       2.54(-)  1.31   0.99 3.03(+)                                                                              2.97 2.15                              90:5:5                                                                        Hex:IPA:CHCl.sub.3                                                                       2.17(-)  1.31   1.15 2.63(+)                                                                              3.31 2.44                              85:5:10                                                                       Hex:IPA:CHCl.sub.3                                                                       1.33(-)  1.31   1.01 1.92(+)                                                                              4.11 2.50                              75:5:20                                                                       Hex:IPA:CHCl.sub.3                                                                       2.72(-)  1.29   0.97 8.99(+)                                                                              --   --                                78:2:20                    (not eluted)                                       ______________________________________                                                 Racemic      Racemic                                                          Compound 9   Compound 10                                                        kl       α                                                                              Rs   kl     α                                                                            Rs                                ______________________________________                                        Hex:IPA 90:10                                                                            2.21(+)  1.49   1.50 1.78(+)                                                                              1.12                                   Hex:IPA:CHCl.sub.3                                                                       2.32(+)  1.49   1.49 1.38(+)                                                                              1.15 0.66                              90:5:5                                                                        Hex:IPA:CHCl.sub.3                                                                       1.60(+)  1.50   1.73 0.89(+)                                                                              1.17 0.63                              85:5:10                                                                       Hex:IPA:CHCl.sub.3                                                                       0.78(+)  1.55   1.80 0.47(+)                                                                              1.20                                   75:5:20                                                                       Hex:IPA:CHCl.sub.3                                                                       1.14(+)  1.54   2.02 2.21(+)                                                                              1.16 1.18                              78:2:20                                                                       ______________________________________                                    

As the relative amount of chloroform to the cellulosetris(4-styrylphenylcarbamate) or tris(4-biphenylylcarbamate) increased,the elution time shortened. Although the α values thereof for theracemic compounds (8), (9) and (10) were improved, those for (5) and(6)- scarcely changed and that for the compound (7) was reduced.

When amylose tris(4-styrylphenylcarbamate) was used, the α values forthe racemic compounds (6), (7)-, (8), (9) and (10) were increased. Whenamylose tris(4-biphenylylcarbamate) was used, the α values for theracemic compounds (6), (8), (9) and (10) were increased. Particularly,the α value was considerably increased when a combination of racemiccompound (8) with amylose tris(4-styrylphenylcarbamate) ortris(4-biphenylylcarbamate) was used.

When hexane/2-propanol/chloroform (78:2:20) was used as the eluent, theelution time for racemic compound (8) was quite long and only oneenantiomer was eluted even after 100 min with cellulosetris(4biphenylylcarbamate), amylose tris(4-styrylphenylcarbamate) oramylose tris(4-biphenylylcarbamate).

For comparison, the results of the resolution obtained by using amylosetriphenylcarbamate as the packing material and varying the proportion ofthe components of the eluent are shown in Table 15. As the relativeamount of chloroform was increased, the elution time was reduced. Thougha slight increase in the A value was observed for racemic compound (8),the values for other racemic compounds were substantially unchanged.

                                      TABLE 15                                    __________________________________________________________________________    Amylose triphenylcarbamate                                                                        Hex:IPA Hex:IPA:CHCl.sub.3                                                                     Hex:IPA:CHCl.sub.3                                                                     Hex:IPA:CHCl.sub.3              Racemic             (90:10) (90:5:5) (85:5:10)                                                                              (75:5:20)                       Compounds           k1   α                                                                          k1   α                                                                           k1   α                                                                           k1   α                    __________________________________________________________________________        ##STR40##       3.72(+)                                                                            ˜1                                                                         4.21(+)                                                                            ˜1                                                                          2.91(+)                                                                            ˜1                                                                          1.60(+)                                                                            ˜1                   6                                                                                 ##STR41##       1.15(-)                                                                            1.53                                                                             2.04(-)                                                                            1.52                                                                              1.69(-)                                                                            1.55                                                                              1.14(-)                                                                            1.55                       8                                                                                 ##STR42##       1.83(+)                                                                            1.52                                                                             4.60(+)                                                                            1.43                                                                              3.92(+)                                                                            1.60                                                                              3.12(+1)                                                                           1.76                       9                                                                                 ##STR43##       1.51(+)                                                                            1.84                                                                             1.61(+)                                                                            1.84                                                                              1.16(+)                                                                            1.85                                                                              0.67(+)                                                                            1.85                       10                                                                                ##STR44##       0.77(+)                                                                            1.28                                                                             0.84(+)                                                                            1.30                                                                              0.58(+)                                                                            1.32                                                                              0.33(+)                                                                            1.31                       __________________________________________________________________________

In Table 16, differences between the α value of the packing materialobtained when hexane/2-propanol/chloroform (75:5:20) was used as theeluent and that obtained when hexane/2-propanol (90:10) was used areshown in parentheses. For comparison, the α values of cellulose andamylose tris(3,5-dimethylphenylcarbamates) having a high opticalresolution capacity are also shown. When the racemic compound (8) andamylose tris(4-biphenylylcarbamate) were used, the α value was thehighest, i.e., 4.11. When the racemic compound (9) and amylosetris(4-biphenylylcarbamate were used, the α value was 1.55 and when theracemic compound (10) and cellulose tris(4-biphenylylcarbamate) wereused, the α value was 1.33, which were far higher than those obtainedwhen cellulose and amylose tris(3,5-dimethylphenylcarbamate) were used.

    TABLE 16      Separation factors (α) on cellulose and amylose triphenylcarbamate      derivatives (General formula for cellulose and amylose derivatives in     Table 10) Cellulose derivatives Amylose derivatives        CompoundsRacem     ic      ##STR45##      ##STR46##      3,5-(CH.sub.3).sub.2.sup.b      ##STR47##      ##STR48##      3,5-(CH.sub.3).sub.2.sup.b                   5      ##STR49##      ˜1 (-0.05) ˜1 (0.00) 1.58 1.19 (-0.01) 1.27 (+0.04) 1.21  6      ##STR50##      1.20 (-0.11) 1.17 (-0.18) 1.83 1.29 (+0.16) 1.31 (-0.04) 2.11  8      ##STR51##      1.22 (+0.22) 1.86 (+0.55) 3.17 3.44 (+0.91) 4.11 (+1.63) 2.01  9      ##STR52##      1.19 (+0.19) 1.48 (+0.28) 1.34 1.54 (+0.23) 1.55 (+0.06) 1.98  10      ##STR53##      1.25 (0.06) 1.33 (+0.08) 1.32 1.19 (+0.10) 1.20 (+0.08) 1.58     a;Eluent, Hex:IPA:CHCl.sub.3 (75:5:20) b;Eluent, Hex:IPA (90:10)

EXAMPLE 15

3 grams of silica gel (RA-227-1) having a particle diameter of 7 μm anda pore diameter of 10 Å which had been surface-treated with3-aminopropyltriethoxysilane was uniformly moistened five times with asolution of 0.75 g of cellulose tris(2-phenylethynylphenylcarbamate) in20-ml of THF, the solution being divided into five portions and eachportion being used each time. The product was sufficiently dried in avacuum line in an evaporator. After the particle size classificationwith hexane/2-propanol, the product was packed in a stainless steelcolumn having a length of 25 cm and an inner diameter of 0.46 cm by theslurry packing method. The number of theoretical stages was 2400 and thedead time was 6.08 min.

A solution of cellulose tris[4-(2-phenylethynyl)phenylcarbamate] in THFwas cast on a slide glass plate and observed with a polarizingmicroscope to reveal that it was crystalline. 0.305 mg/μl solution ofcellulose tris[4-(2-phenylethynyl)phenylcarbamate] in THF was preparedand the liquid-crystal property thereof was examined. The solution wasgreen, since cellulose tris[4-(2-phenylethynyl)phenylcarbamate] per sewas a green polymer. After a few days, the solution was slightly pearly.

Though the exact σ-value of ##STR54## was unknown, it was supposedly aweakly electron-attractive group, since acetone elution time thereof was10.97 min.

It was supposed that when chloroform was added to the eluent, chloroformsurrounded the phenyl group owing to the interaction between chloroformand the phenyl group to change the resolution power. Therefore,hexane/2-propanol/chloroform (90:5:5) was used as the eluent. As aresult, the resolution power was higher than that of hexane/2-propanol(90:10), though the extent of the increase varied depending on thecompounds such as ##STR55## On the contrary, the resolution power for##STR56## and Troger base was reduced (see Table 17).

                                      TABLE 17                                    __________________________________________________________________________    The results of optical resolution with cellulose                              tris [4-(2-phenylethynyl)phenylcarbamate] at 25° C.                                      Hex:IPA     Hex:IPA:CHCl.sub.1                                                90:10       90:5:5                                          Racemate          K'    α                                                                          RS K' α                                                                            RS                                      __________________________________________________________________________     ##STR57##        1.31(-)                                                                             1.27                                                                             0.58                                                                             2.21                                                                             1.14                                          ##STR58##        2.46(-0                                                                             1.46  6.48                                                                             1.57 1.66                                     ##STR59##        4.17(-)                                                                             1.94                                                                             2.60                                               Troger base       2.11(+)                                                                             1.13                                                                             0.72                                                                             1.01                                                                             1.07                                          ##STR60##        333(-)                                                                              1.09  3.23                                                                             1.10 1.02                                     ##STR61##        0.84(+)                                                                             1.68                                                                             2.83                                                                             0.73                                                                             2.00 3.89                                     ##STR62##        1.18(-)                                                                             1.20                                                                             0.75                                                                             1.99                                                                             1.30 1.95                                     ##STR63##        2.25(+)                                                                             1.50                                                                             2.58                                                                             1.28                                                                             1.69 2.55                                    Co(acac).sub.3    7.82(30 )                                                                           1.41                                                                             2.29                                               Cr(acac).sub.3    5.82(-)                                                                             1.54                                                                             1.95                                                                             2.52                                                                             1.56 1.94                                     ##STR64##        2.75(-)                                                                             1.14                                                                             0.79                                                                             1.35                                                                             1.16 1.02                                     ##STR65##        6.29(-)                                                                             1.25                                                                             2.57                                                                             6.99                                                                             1.27 2.63                                     ##STR66##        10.02(+)                                                                            1.02  4.16                                                                             1.04                                         __________________________________________________________________________

EXAMPLE 16

Silica gel (RA 227-1) having a particle diameter of 7 μm and a porediameter of 4000 Å which had been surface-treated with3-aminopropyltriethoxysilane was used. 0.75 grams of cellulosetris(4-phenoxyphenylcarbamate) was dissolved in 10 ml of THF. 3.02 gramsof the surface-treated silica gel (RA 227-1) was uniformly moistenedwith about 2.5 ml of THF Solution and then sufficiently dried in avacuum line in an evaporator. This procedure was repeated four times.0.76 g of amylose tris(4-phenoxyphenylcarbamate) was dissolved in 10 mlof THF. The same treatment as that of cellulosetris(4-phenoxyphenylcarbamate) was conducted except that 3.02 grams ofRA 227-1 was used.

The packing material prepared in the above step was subjected toparticle size classification with hexane/2-propanol and packed in astainless steel column having a length of 25 cm and an inner diameter of0.46 cm by the slurry packing method.

When 0.5 ml/min of hexane/2-propanol (90:10) (25° C.) was used as theeluent, the number of theoretical plates for benzene was 2700 [cellulosetris(4-phenoxyphenylcarbamate)] and 3000 [amylosetris(4-phenoxyphenylcarbamate)].

Cellulose tris(4-phenoxyphenylcarbamate) formed liquid crystals in THF.The high crystallinity of this compound was confirmed by casting on aglass plate followed by observation with a polarizing microscope.Amylose carbamate was also cast from THF and observed with a polarizingmicroscope to reveal that it formed no liquid crystals, though it formedcrystals.

Since both compounds were highly soluble in chloroform,hexane/2-propanol (90:10) free from chloroform was used as the eluent.

In the results of the resolution obtained with cellulosetris(4-phenoxyphenylcarbamate), the resolution result for racemiccompound 13 was better (α=1.53) than those obtained with cellulosetris(3,5 dimethylphenylcarbamate) and cellulose tris(3,5dichlorophenylcarbamate) and α values for racemic compounds 15 and 16were as high as 1.81 and 1.72, respectively. It is apparent from Table18 that the α values for racemic compounds 16, 17 and ##STR67## werequite as high as 1.72, 3.04 and 1.32, respectively. Thus, highresolution capacities were obtained when the anilide compounds wereused. The α values, for ##STR68## was 1.29.

In the results of the resolution obtained with amylosetris(4-phenoxyphenylcarbamate), the racemic compounds which could not beresolved with amylose tris(3,5 dimethylphenylcarbamate) and amylosetris(3,5 dichlorophenylcarbamate) could be resolved with amylosetris(4-phenoxyphenylcarbamate), though the α values were low (α=1.08 and1.16, respectively). In the results of the resolution of racemiccompounds 8 and 13, excellent resolution results (α=2.24) and 2.12) wereobtained.

                                      TABLE 18                                    __________________________________________________________________________    The results of resolution with 1 and 4                                                                     Amylose                                                                       tris(4-phenoxyphenyl-                            Cellulose tris(4-phenoxyphenylcarbamate)                                                                    carbamate)                                      Racemate          K'   α                                                                          RS K'   α                                                                          RS                                       __________________________________________________________________________     ##STR69##      7 1.44(-)                                                                            1.15  1.21(-)                                                                            1.55                                                                             1.31                                      ##STR70##      2 0.82(+)                                                                            1.37                                                                             1.70                                                                             0.74(+)                                                                            2.24                                                                             3.75                                      ##STR71##      9 4.78(-)                                                                            1.10                                                                             0.77                                                                             5.51(+)                                                                            1.19                                                                             1.40                                     Troger base     10                                                                              1.75(-)                                                                            ˜1                                                                            1.42(+)                                                                            1.55                                                                             1.75                                      ##STR72##      11                                                                              3.07(-)                                                                            1.15                                                                             1.46                                                                             2.76(+)                                                                            1.04                                         ##STR73##      12                                                                              1.00(-)                                                                            1.33                                                                             1.31                                                                             0.85(+)                                                                            1.11                                         ##STR74##      13                                                                              1.92(+)                                                                            1.53                                                                             1.61                                                                             2.39(+)                                                                            2.12                                                                             2.24                                      ##STR75##      14                                                                              1.94(-)                                                                            1.12                                                                             0.67                                                                             1.66(+)                                                                            1.08                                        Co(acac).sub.3  15                                                                              1.68(+)                                                                            1.81                                                                             1.72                                                                             1.66(+)                                                                            1.16                                         ##STR76##      16                                                                              2.14(-)                                                                            1.72                                                                             1.21                                                                             1.49(+)                                                                            1.32                                         ##STR77##      17                                                                              4.03(-)                                                                            3.04                                                                             3.16                                                                             2.90(+)                                                                            1.70                                        Cr(acac).sub.3  18                                                                              2.08(+)                                                                            2.27                                                                             3.31                                                                             1.41(+)                                                                            1.15                                         ##STR78##      19                                                                              1.11(-)                                                                            1.15  1.34(-)                                                                            1.09                                         ##STR79##      20                                                                              1.55(-)                                                                            ˜1                                                                            1.18(+)                                                                            ˜1                                    __________________________________________________________________________

                                      TABLE 19                                    __________________________________________________________________________    The results of resolution with cellulose derivatives                          tris (4-phenoxy  tris (3,5 dimethyl                                                                       tris (3,5 dichloro-                               phenylcarbamate) phenylcarbamate)                                                                         phenylcarbamate)                                  Racemate                                                                            kl   α                                                                          R.sub.s                                                                          kl   α                                                                          R.sub.s                                                                          kl   α                                                                          R.sub.s                                   __________________________________________________________________________     7    1.44(-)                                                                            1.15  2.36(-)                                                                            1.83                                                                             4.39                                                                             1.62(+)                                                                            1.11                                                                             0.75                                       8    0.82(+)                                                                            1.37                                                                             1.70                                                                             0.74(-)                                                                            1.68                                                                             3.22                                                                             0.56(+)                                                                            1.84                                                                             4.20                                       9    4.78(-)                                                                            1.10                                                                             0.77                                                                             2.43(+)                                                                            1.58                                                                             4.38                                                                             3.08(-)                                                                            1.21                                                                             1.91                                      10    1.75(-)                                                                            ˜1                                                                            0.98(+)                                                                            1.32                                                                             1.92                                                                             0.87(+)                                                                            1.65                                                                             3.89                                      11    3.07(-)                                                                            1.15                                                                             1.46                                                                             1.47(-)                                                                            1.41                                                                             3.08                                                                             1.55(-)                                                                            1.20                                                                             1.48                                      12    1.00(-)                                                                            1.33                                                                             1.31                                                                             2.13(-)                                                                            2.59                                                                             6.40                                                                             0.28(-)                                                                            1.38                                                                             0.87                                      13    1.92(+)                                                                            1.53                                                                             1.61                                                                             1.37(+)                                                                            1.34                                                                             1.87                                                                             0.40(+)                                                                            1.29                                                                             0.84                                      14    1.94(-)                                                                            1.12                                                                             0.67                                                                             1.17(-)                                                                            1.15                                                                             0.90                                                                             2.65(-)                                                                            1.26                                                                             1.95                                      15    1.68(+)                                                                            1.81                                                                             1.72                                                                             0.42(+)                                                                            ˜1                                                                            0.76(+)                                                                            1.82                                                                             4.06                                      16    2.14(-)                                                                            1.72                                                                             1.21                                                                             0.83(+)                                                                            3.17                                                                             6.17                                                                             0.59(+)                                                                            1.41                                                                             1.47                                      __________________________________________________________________________

                                      TABLE 20                                    __________________________________________________________________________    The results of resolution with amylose derivatives                            tris (4-phenoxy  tris (3,5 dimethyl                                                                       tris (3,5 dichloro-                               phenylcarbamate) phenylcarbamate)                                                                         phenylcarbamate)                                  Racemate                                                                            kl   α                                                                          R.sub.s                                                                          kl   α                                                                          R.sub.s                                                                          kl   α                                                                          R.sub.s                                   __________________________________________________________________________     7    1.21(-)                                                                            1.55                                                                             1.31                                                                             2.46(-)                                                                            2.11                                                                             6.38                                                                             1.10(+)                                                                            ˜1                                      8    0.74(+)                                                                            2.24                                                                             3.75                                                                             0.42(+)                                                                            3.04                                                                             6.67                                                                             0.50(+)                                                                            1.32                                                                             1.69                                       9    5.51(+)                                                                            1.19                                                                             1.40                                                                             3.14(-)                                                                            1.21                                                                             2.07                                                                             6.08(+)                                                                            ˜1                                     10    1.42(+)                                                                            1.55                                                                             1.75                                                                             0.53(+)                                                                            1.58                                                                             2.30                                                                             0.84(+)                                                                            1.34                                                                             2.27                                      11    2.76(?)                                                                            1.04  0.93(+)                                                                            1.12                                                                             0.77                                                                             1.62(+)                                                                            1.10                                                                             1.02                                      12    0.85(+)                                                                            1.11  1.30(+)                                                                            1.15                                                                             0.75                                                                             0.37 1.00                                         13    2.39(+)                                                                            2.12                                                                             2.24                                                                             2.65(+)                                                                            1.98                                                                             5.48                                                                             0.88(+)                                                                            2.25                                                                             6.05                                      14    1.66(+)                                                                            1.08  0.61(-)                                                                            ˜1                                                                            1.26(-)                                                                            ˜1                                     15    1.66(-)                                                                            1.16  0.25(-)                                                                            ˜1                                                                            0.63(+)                                                                            ˜1                                     16    1.19(+)                                                                            1.32  3.25(+)                                                                            2.01                                                                             3.59                                                                             0.59(-)                                                                            1.11                                         __________________________________________________________________________

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:
 1. A separating agent whichcomprises particles having a particle size of 1 micron to 10 mm andessentially consisting of a polysaccharide derivative having 30-100% ofthe hydroxyl groups thereof substituted with a substituent selected fromthe group consisting of an acyl group of the formula (1): ##STR80##wherein R represents an atomic group having a nucleus comprising aconjugated pi-bond system in which the number of bonds interposedbetween (1) a first atom contained in said atomic group and bonded withthe carbonyl and (2) a second atom contained in the pi-bond system andmost distant from said first atom is at least 5 by the shortest route,wherein said polysaccharide derivative is cellulose tri-β-naphthoate. 2.A separating agent which comprises a carrier having a particle size of 1micron to 10 mm and a pore size of 10 A to 100 microns and apolysaccharide derivative having 30-100% of the hydroxyl groups thereofsubstituted with a substituent selected from the group consisting of anacyl group of the formula (1): ##STR81## wherein R represents an atomicgroup having a nucleus comprising a conjugated pi-bond system in whichthe number of bonds interposed between (1) a first atom contained insaid atomic group and bonded with the carbonyl and (2) a second atomcontained in the pi-bond system and most distant from said first atom isat least 5 by the shortest route, wherein said polysaccharide derivativeis cellulose tri-β-naphthoate.